Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Nonstoichiometry, Defect Chemistry and Oxygen Transport in Fe-Doped Layered Double Perovskite Cobaltite PrBaCo2-xFexO6-δ (x = 0-0.6) Membrane Materials.

ABSTRACT: Mixed conducting cobaltites PrBaCo2-xFexO6-δ (x = 0-0.6) with a double perovskite structure are promising materials for ceramic semi-permeable membranes for oxygen separation and purification due to their fast oxygen exchange and diffusion capability. Here, we report the results of the detailed study of an interplay between the defect chemistry, oxygen nonstoichiometry and oxygen transport in these materials as a function of iron doping. We show that doping leads to a systematic variation of both the thermodynamics of defect formation reactions and oxygen transport properties. Thus, iron doping can be used to optimize the performance of mixed conducting oxygen-permeable double perovskite membrane materials.

SUBMITTER: Ivanov IL

PROVIDER: S-EPMC9783566 | biostudies-literature | 2022 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Nonstoichiometry, Defect Chemistry and Oxygen Transport in Fe-Doped Layered Double Perovskite Cobaltite PrBaCo2-xFexO6-δ (x = 0-0.6) Membrane Materials.

Ivanov Ivan L IL Zakiryanov Petr O PO Sereda Vladimir V VV Mazurin Maxim O MO Malyshkin Dmitry A DA Zuev Andrey Yu AY Tsvetkov Dmitry S DS

Membranes 20221128 12

Mixed conducting cobaltites PrBaCo2-xFexO6-δ (x = 0-0.6) with a double perovskite structure are promising materials for ceramic semi-permeable membranes for oxygen separation and purification due to their fast oxygen exchange and diffusion capability. Here, we report the results of the detailed study of an interplay between the defect chemistry, oxygen nonstoichiometry and oxygen transport in these materials as a function of iron doping. We s ...[more]

PMID: 36557108

Similar Datasets

Effect of A-Site Nonstoichiometry on Defect Chemistry and Electrical Conductivity of Undoped and Y-Doped SrZrO3.

Project description:The effect of Sr-nonstoichiometry on phase composition, microstructure, defect chemistry and electrical conductivity of SrxZrO3-δ and SrxZr0.95Y0.05O3-δ ceramics (SZx and SZYx, respectively; x = 0.94-1.02) was investigated via X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy and impedance spectroscopy followed by distribution of relaxation times analysis of impedance data. It was shown that at low Sr deficiency (x > 0.96 and 0.98 for SZx and SZYx, respectively) a solid solution of strontium vacancies in strontium zirconate crystal structure forms, whereas at higher Sr deficiency the secondary phase, zirconium oxide or yttrium zirconium oxide, is precipitated. Yttrium solubility limit in strontium zirconate was found to be close to 2 mol%. Y-doped strontium zirconates possess up to two orders of magnitude higher total conductivity than SZx samples. A-site nonstoichiometry was shown to have a significant effect on the electrical conductivity of SZx and SZYx. The highest total and bulk conductivity were observed at x = 0.98 for both systems. Increasing the conductivity with a rise in humidity indicates that proton conduction appears in the oxides in wet conditions. A defect model based on consideration of different types of point defects, such as strontium vacancies, substitutional defects and oxygen vacancies, and assumption of Y ions partitioning over Zr and Sr sites was elaborated. The proposed model consistently describes the obtained data on conductivity.

| S-EPMC6514593 | biostudies-literature

Preparation and bifunctional properties of the A-site-deficient SrTi0.3Fe0.6Ni0.1O3-δ perovskite.

Project description:The development of efficient, non-noble metal electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is crucial for their application in energy storage devices, such as fuel cells and metal-air batteries. In this study, SrTi0.3Fe0.6Ni0.1O3-δ (STFN) perovskite was synthesized using the sol-gel method, and its electrocatalytic activity was evaluated using a rotating disk electrode (RDE) in an alkaline medium. STFN synthesized at the optimum synthesis temperature of 800 °C exhibited good ORR and OER performances. To further improve electrocatalytic activity, a series of Sr1-x Ti0.3Fe0.6Ni0.1O3-δ (x = 0, 0.05, and 0.1) perovskites with A-site vacancies were synthesized at 800 °C. Material characterization results showed that the removal of the A-site from the perovskite led to an increase in surface oxygen vacancies, resulting in higher ORR and OER activities. The results of this study indicate that Sr1-x Ti0.3Fe0.6Ni0.1O3-δ (x = 0.1) is a promising bifunctional oxygen electrocatalyst for Zn-air batteries.

| S-EPMC9703302 | biostudies-literature

Random fields and apparent exchange bias in the dilute Ising antiferromagnet Fe0.6Zn0.4F2.

Project description:Random field induced spontaneous excess moments appear in field cooled single crystals of diluted Ising antiferromagnets. Here we report results from low temperature measurements of field cooled (including zero field) magnetic hysteresis loops parallel and perpendicular to the c-axis of a single crystal of composition Fe0.6Zn0.4F2. We find that weak static ferromagnetic excess moments attained on field cooling give rise to an apparent exchange bias of the magnetic hysteresis loops, whose magnitude is controlled by temperature and the strength and direction of the cooling field. Random field induced temporal excess moments only become observable in cooling fields larger than 1 T applied along the c-axis direction of the Fe0.6Zn0.4F2 single crystal.

| S-EPMC7471909 | biostudies-literature

Toward a Consistent Prediction of Defect Chemistry in CeO2.

Project description:Polarizable shell-model potentials are widely used for atomic-scale modeling of charged defects in solids using the Mott-Littleton approach and hybrid Quantum Mechanical/Molecular Mechanical (QM/MM) embedded-cluster techniques. However, at the pure MM level of theory, the calculated defect energetics may not satisfy the requirement of quantitative predictions and are limited to only certain charged states. Here, we proposed a novel interatomic potential development scheme that unifies the predictions of all relevant charged defects in CeO2 based on the Mott-Littleton approach and QM/MM electronic-structure calculations. The predicted formation energies of oxygen vacancies accompanied by different excess electron localization patterns at the MM level of theory reach the accuracy of density functional theory (DFT) calculations using hybrid functionals. The new potential also accurately reproduces a wide range of physical properties of CeO2, showing excellent agreement with experimental and other computational studies. These findings provide opportunities for accurate large-scale modeling of the partial reduction and nonstoichiometry in CeO2, as well as a prototype for developing robust interatomic potentials for other defective crystals.

| S-EPMC9835833 | biostudies-literature

Fabrication, defect chemistry and microstructure of Mn-doped UO2.

Project description:Mn-doped UO2 is under consideration for use as an accident tolerant nuclear fuel. We detail the synthesis of Mn-doped UO2 prepared via a wet co-precipitation method, which was refined to improve the yield of incorporated Mn. To verify the Mn-doped UO2 defect chemistry, X-ray absorption spectroscopy at the Mn K-edge was performed, in addition to X-ray diffraction, Raman spectroscopy and high-energy resolved fluorescence detection X-ray absorption near edge spectroscopy at the U M4-edge. It was established that Mn2+ directly substitutes for U4+ in the UO2 lattice, accompanied by oxygen vacancy (Ov) charge compensation. In contrast to other divalent-element doped UO2 materials, compelling evidence for U5+ in a charge compensating role was not found. This work furthers understanding of the structure and crystal chemistry of Mn-doped UO2, which could show potential advantages as a novel efficient advanced nuclear fuel.

| S-EPMC10796358 | biostudies-literature

Defect Chemistry and Li-ion Diffusion in Li2RuO3.

Project description:Layered Li2RuO3 is an important candidate cathode material in rechargeable lithium ion batteries because of its novel anionic redox process and high reversible capacity. Atomistic scale simulations are used to calculate the intrinsic defect process, favourable dopants and migration energies of lithium ion diffusions together with migration paths in Li2RuO3. The Li Frenkel is calculated to be the most favourable intrinsic defect type. The cation anti-site defect, in which Li and Ru ions exchange their positions is 1.89 eV/defect suggesting that this defect would be observed at high temperatures. Long range vacancy assisted lithium diffusion paths were calculated and it is confirmed that the lowest overall activation energy (0.73 eV) migration path is along the ab plane. Trivalent dopants (Al3+, Co3+, Sc3+, In3+, Y3+, Gd3+ and La3+) were considered to create additional Li in Li2RuO3. Here we show that Al3+ or Co3+ are the ideal dopants and this is in agreement with the experimental studies reported on Co3+ doping in Li2RuO3.

| S-EPMC6345755 | biostudies-literature

Exciton-phonon coupling in two-dimensional layered (BA)2PbI4 perovskite microplates.

Project description:Two-dimensional layered (BA)2PbI4 (BA = C4H9NH3) perovskites are emerging as a new class of layered materials and show great potential in optoelectronic applications. Elucidating how exciton-phonon interaction affects the excitonic emission is of great importance for a better knowledge of their optoelectronic properties. In this letter, we synthesized high-quality (BA)2PbI4 microplates via solution methods, and dual-excitonic emission peaks (surface-emission and interior-emission) were detected from the as-grown samples at low temperatures. Furthermore, we determine the energies for the longitudinal optical phonon modes to be ∼27 and ∼18 meV, and the exciton-phonon coupling strengths to be ∼177 and ∼21 meV for the surface-emission and interior-emission bands, respectively. Compared to the interior-emission band, the stronger exciton-phonon interaction results in a considerable degree of spectral broadening and red-shift for the surface-emission with increasing temperature. In contrast, the (OA)2PbI4 (OA = C8H17NH2) microplates with longer alkyl chains between Pb-I layers, exhibit only one excitonic emission peak, as well as a large exciton-phonon coupling strength. Our work clarifies the influence of exciton-phonon coupling on the excitonic emission of (BA)2PbI4 microplates, and also suggests the intrinsic relationship between the exciton-phonon coupling and the length of organic carbon chain ligands.

| S-EPMC9936372 | biostudies-literature

Influence of intrinsic spin ordering in La0.6Sr0.4Co0.8Fe0.2O3-δ and Ba0.6Sr0.4Co0.8Fe0.2O3-δ towards electrocatalysis of oxygen redox reaction in solid oxide cell.

Project description:The redox reaction of oxygen (OER & ORR) forms the rate determining step of important processes like cellular respiration and water splitting. Being a spin relaxed process governed by quantum spin exchange interaction, QSEI (the ground triplet state in O2 is associated with singlet oxygen in H2O/OH-), its kinetics is sluggish and requires inclusion of selective catalyst. Functionality and sustainability of solid oxide cell involving fuel cell (FC) and electrolyzer cell (EC) are also controlled by ORR (oxygen redox reaction) and OER (oxygen evolution reaction). We suggest that, presence of inherent spin polarization within La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF6482) (15.86 emu g-1) and Ba0.6Sr0.4Co0.8Fe0.2O3-δ (BSCF6482) (3.64 emu g-1) accounts for the excellent selective electrocatalysis towards ORR and OER. QSEI forms the atomic level basis for OER/ORR which is directly proportional to spin ordering (non-zero magnetization) of the active electrocatalyst. LSCF6482 exhibits (21.5 kJ mol-1@0.8 V for ORR compared to 61 kJ mol-1@0.8 V for OER) improved ORR kinetics whereas BSCF6482 (18.79 kJ mol-1@0.8 V for OER compared to 32.19 kJ mol-1 for ORR@-0.8 V) is best suited for OER under the present stoichiometry. The findings establish the presence of inherent spin polarization of catalyst to be an effective descriptor for OER and ORR kinetics in solid oxide cell (SOC).

| S-EPMC11422708 | biostudies-literature

Evolving Defect Chemistry of (Pu,Am)O2±x.

Project description:The β decay of 241Pu to 241Am results in a significant ingrowth of Am during the interim storage of PuO2. Consequently, the safe storage of the large stockpiles of separated Pu requires an understanding of how this ingrowth affects the chemistry of PuO2. This work combines density functional theory (DFT) defect energies and empirical potential calculations of vibrational entropies to create a point defect model to predict how the defect chemistry of PuO2 evolves due to the incorporation of Am. The model predicts that Am occupies Pu sites in (Pu,Am)O2±x in either the +III or +IV oxidation state. High temperatures, low oxygen-to-metal (O/M) ratios, or low Am concentrations favor Am in the +III oxidation state. Am (+III) exists in (Pu,Am)O2±x as the negatively charged (AmPu 1-) defect, requiring charge compensation from holes in the valence band, thereby increasing the conductivity of the material compared to Am-free PuO2. Oxygen vacancies take over as the charge compensation mechanism at low O/M ratios. In (Pu,Am)O2±x , hypo- and (negligible) hyperstoichiometry is found to be provided by the doubly charged oxygen vacancy (VO 2+) and singly charged oxygen interstitial (Oi 1-), respectively.

| S-EPMC8392350 | biostudies-literature

Engineering electrocatalytic activity in nanosized perovskite cobaltite through surface spin-state transition.

Project description:The activity of electrocatalysts exhibits a strongly dependence on their electronic structures. Specifically, for perovskite oxides, Shao-Horn and co-workers have reported a correlation between the oxygen evolution reaction activity and the eg orbital occupation of transition-metal ions, which provides guidelines for the design of highly active catalysts. Here we demonstrate a facile method to engineer the eg filling of perovskite cobaltite LaCoO3 for improving the oxygen evolution reaction activity. By reducing the particle size to ∼80 nm, the eg filling of cobalt ions is successfully increased from unity to near the optimal configuration of 1.2 expected by Shao-Horn's principle. Consequently, the activity is significantly enhanced, comparable to those of recently reported cobalt oxides with eg(∼1.2) configurations. This enhancement is ascribed to the emergence of spin-state transition from low-spin to high-spin states for cobalt ions at the surface of the nanoparticles, leading to more active sites with increased reactivity.

| S-EPMC4873645 | biostudies-literature